Supplementary Material

Table SI-1: Experimentally determined retention times of all analyzed components, and if they are present as solids at 298 K, the
solvents used. All retention times were measured at a flow rate of 0.6 ml/min as well as at 308 K column and 298 K measuring
cell temperature.

Components Solvent Retention time [min]

Water - 6.5
Choline chloride (ChCl) Water 6.5
Tetraethyl ammonium chloride (TEAC) Water 6.6
Tetrabutyl ammonium chloride (TBAC) Water 6.7
Fructose Water 9.8
Lactic acid (LAA) - 13.7
Levulinic acid (LA) - 17.4
5-hydroxymethylfurfural (HMF) Water 36.3
Standard uncertainity: u(V) = 10 µl/min.
Table SI-2: 5-Hydroxymethylfurfural (HMF) yields in choline chloride:water (ChCl:W), levulinic acid (LA), and choline
chloride:levulinic acid (ChCl:LA); reaction temperature: 323 K; fructose starting concentration: 2.5 wt.%; pressure: 1 bar.

time [h] ChCl:W LA ChCl:LA

YHMF [%] SD [%] YHMF [%] SD [%] YHMF [%] SD [%]
(a)
1 - - - - 8.31
(a)
2 - - - - 10.31
(a)
3 - - - - 12.18
48 0.00 0.00 14.14 0.00 22.70 1.03
121 - - 14.38 0.00 36.25 2.54
165 0.00 0.00 13.86 0.00 51.71 0.44
288 - - 11.74 4.08 57.19 0.73
332 - - - - 57.46 0.13
(a)
Due to the short time between sampling and the duration of the HPLC analysis, the samples were analyzed only once.
Accordingly, no standard deviation could be calculated.
Standard uncertainty: u(m) = 0.15 mg; u(wH2O) = 0.03; u(T) = 0.5 K; u(YHMF) = 1.7 %.

Table SI-3: The different deep eutectic systems (DESs), each composed of a hydrogen bond acceptor (HBA) and one of the
two carboxylic acids: lactic acid (LAA) and levulinic acid (LA). The maximum 5-hydroxymethylfurfural (HMF) yields are
listed in ascending order from left to right. In addition, the pH measured in the various DESs is documented.

HBA TBAC ChCl TEAC

HBD LAA LA LAA LA LAA LA
YHMF [%] 40.6 47.8 52.6 57.5 59.6 68.1
pH [-] 0.83 1.71 0.48 1.62 1.37 2.92
Standard uncertainty: u(m) = 0.15 mg; u(wH2O) = 0.03; u(T) = 0.5 K; u(YHMF) = 1.7 %; u(pH) = 0.02.
Table SI-4: 5-Hydroxymethylfurfural (HMF) yields in deep eutectic systems consisting out of tetraethyl ammonium chloride with
levulinic (LA) or lactic acid (LAA) in a molar ratio of 1:2; reaction temperature: 323 K; fructose starting concentration: 2.5 wt.%;
pressure: 1 bar.

time TEAC:LA TEAC:LAA

[h] YHMF [%] SD [%] YHMF [%] SD [%]
(a)
1 6.92 - -
(a)
2 7.46 - -
(a)
3 8.36 - -
48 44.94 1.19 29.42 1.53
121 68.11 - 57.04 3.68
288 67.04 2.76 - -
312 - - 59.06 5.79
332 66.81 2.12 - -
350 - - 59.55 4.92
(a)
Due to the short time between sampling and the duration of the HPLC analysis, the samples were analyzed only once. Accordingly,
no standard deviation could be calculated.
Standard uncertainty: u(m) = 0.15 mg; u(wH2O) = 0.03; u(T) = 0.5 K; u(YHMF) = 1.7 %.

Table SI-5: 5-Hydroxymethylfurfural (HMF) yields in deep eutectic systems based on levulinic acid (LA) in a molar ratio of 1:2;
reaction temperature: 323 K; fructose starting concentration: 2.5 wt.%; pressure: 1 bar.

time ChCl:LA TBAC:LA TEAC:LA

[h]
YHMF [%] SD [%] YHMF [%] SD [%] YHMF [%] SD [%]
(a) (a) (a)
1 8.31 5.32 6.92
(a) (a) (a)
2 10.31 5.32 7.46
(a) (a) (a)
3 12.18 5.42 8.36
48 22.70 1.03 15.99 0.67 44.94 1.19
121 36.25 2.54 - - 68.11 -
165 51.71 0.44 44.20 0.74 - -
288 57.19 0.73
Table SI-6: 5-Hydroxymethylfurfural (HMF) yields in47.76 0.84
deep eutectic systems 67.04
based on lactic acid (LAA) in a molar2.76
ratio of 1:2;
reaction temperature: 323 K; fructose starting concentration: 2.5 wt.%; pressure: 1 bar.
332 57.46 0.13 47.80 3.42 66.81 2.12
time
(a)
Due to the short timeChCl:LAA TBAC:LAA
between sampling and the duration of the HPLC analysis, the samples were TEAC:LAA
analyzed only once.
[h]
Accordingly, no standard deviation could be calculated.
YHMF [%]
Standard uncertainty:
SD [%] Y u(T)[%]
u(m) = 0.15 mg; u(wH2O) = 0.03;HMF
SD [%]
= 0.5 K; u(YHMF) = 1.7 %.
YHMF [%] SD [%]
48 22.12 2.86 24.95 1.83 29.42 1.53
121 28.72 0.88 40.23 0.73 57.04 3.68
168 41.07 0.39 - - - -
312 52.61 1.73 40.65 1.18 59.06 5.79
350 52.07 1.71 40.54 1.45 59.55 4.92
Standard uncertainty: u(m) = 0.15 mg; u(wH2O) = 0.03; u(T) = 0.5 K; u(YHMF) = 1.7 %.
Table SI-7: 5-Hydroxymethylfurfural (HMF) yields in the deep eutectic system tetraethyl ammonium chloride:levulinic
acid (TEAC: LA) in a molar ratio of 1:2 with various catalysts added directly (in powder form); reaction temperature: 323 K;
fructose starting concentration: 2.5 wt.%; catalyst concentration: 4.0 wt.%; pressure: 1 bar.

time TEAC:LA+NH4VO3 TEAC:LA+VOSO4 TEAC:LA+HPA-5

[h]
YHMF [%] SD [%] YHMF [%] SD [%] YHMF [%] SD [%]
(a) (a) (a)
1 4.89 16.66 3.65
(a)
5 - - - - 57.16
(a) (a) (a)
24 3.00 45.47 57.67
(a) -
30 2.62 - - -
(a) (a) -
48 2.55 45.82 -
(a) - -
72 1.71 - -
(a) -
170 1.84 - - -
(a)
Due to the short time between sampling and the duration of the HPLC analysis, the samples were analyzed only once.
Accordingly, no standard deviation could be calculated.
Standard uncertainty: u(m) = 0.15 mg; u(wH2O) = 0.03; u(T) = 0.5 K; u(YHMF) = 1.7 %.

Table SI-8: Manufacturer, purity and CAS-number of the used chemicals.

Name Manufacturer Purity [wt.%] CAS-number

Acetonitrile VWR International 99.9 75-05-8
Choline chloride Sigma Aldrich 98.0 67-48-1
(a) (a)
CombiTitrant 5 Merck KGaA
D-(-)-fructose Sigma Aldrich 99+ 57-48-7
Dimethyl sulfoxide Merck KGaA 99.9 67-68-5
5-(Hydroxymethyl)furfural Molekula 99.1 67-47-0
Levulinic acid Sigma Aldrich 98.0 123-76-2
Malonic acid Alfa Aesar 99+ 141-82-2
(-)-Menthol Tokyo Chemical Industry 99+ 2216-51-5
Methanol Merck KGaA 99.9 67-56-1
DL-lactic acid Sigma Aldrich ~90(b) 50-21-5
L-lactic acid (anhydrous) Alfa Aesar 98.0 79-33-4
(c) (c)
Deionized water Merck KGaA
Oxalic acid Sigma Aldrich 98.0 144-62-7
Sulfuric acid VWR International 99.9(d) 7664-93-9
Tetrabutyl ammonium chloride Carbolution 98.0 1112-67-0
Tetraethyl ammonium chloride Alfa Aesar 98.0 56-34-8
Thymol Tokyo Chemical Industry 99.9 89-83-8
(a)
No information available from Merck KGaA.
(b)
According to Sigma Aldrich; according to Karl Fischer titration, however, 86.9%.
(c)
A 0.22 μm membrane filter (Millipak Express, Merck KGaA, Darmstadt, Germany) ensures particle- and
bacteria-free water.
(d)
0.1 mol / l sulfuric acid.
Table SI-9: Experimental measured solubility of fructose (298 K, 1 bar) in DESs and water content of the DESs.

DES xfructose xwater

[mol/mol]a [mol/mol] b

ChCl:LA 0.0257 0.123

TBAC:LA 0.0391 0.127

TEAC:LA 0.0303 0.093

ChCl:LAA 0.0806 0.306

TBAC:LAA 0.0360 0.197

TEAC:LAA 0.0479 0.264

a: mol/(mol DES+fructose) b: mol/(mol DES+water)

Figure SI-1: HPLC chromatogram (RI – refractive index) of a reaction mixture after a reaction time of 288 hours without
additional catalyst. Reaction from fructose to HMF at 323.15 K and 1 bar in the DES TEAC:LA. The peaks belong to
tetraethyl ammonium chloride (TEAC; 6.598 min), levulinic acid (LA at 17.666 min) and 5-hydroxymethylfurfural
(HMF at 37.394 min). TEAC and water (at 6.906 min) could not be separated by the applied HPLC method. Neither
fructose (the substrate; retention time about 9.5 min) nor any other side products were detected.
Figure SI-2: HPLC chromatogram (RI – refractive index) of a reaction mixture after a reaction time of 5 hours containing
catalyst HPA-5. Reaction from fructose to HMF at 323.15 K and 1 bar in the DES TEAC:LA. The peaks belong to
tetraethyl ammonium chloride (TEAC; 6.612 min), levulinic acid (LA at 17.186 min) and 5-hydroxymethylfurfural
(HMF at 36.200 min). TEAC and water (at 6.945 min) could not be separated by the applied HPLC method. Neither
fructose (the substrate; retention time about 9.5 min) nor any other side products were detected.

Figure SI-3: Solid-liquid equilibrium between HBD and choline chloride (ChCl) at 1 bar. Red: HBD = levulinic acid (LA),
this work. Blue: HBD = DL-lactic acid (LAA), results from literature [29]. Symbols are experimental data (circles: ChCl
solubility; triangles: HBD solubility), lines are PC-SAFT predictions using the parameters from ref s.[27, 28] without using
any binary interaction parameters. Solubility modeling required fusion data: enthalpy of fusion (4300 J/mol for ChCl;
11340 J/mol for LAA; 17136 J/mol for LA) and melting temperature (597 K for ChCl; 306 K for LA; 289 K for LAA);
heat capacity differences between solid and liquid phase were set to zero for solubility modeling.
Figure SI-4: Coloring of samples of reaction mixtures at 323 K after 1 hour (left sample) and after 48 hours (right sample). The
starting weight fraction of fructose was 2.5 w% in the DES tetraethyl ammonium chloride:levulinic acid (TEAC:LA 1:2). Catalyst
HPA-5 was added to the reaction mixture undissolved as a powder. The brownish color denotes to the formation of side products,
i.e. especially humins.

Figure SI-5: 5-Hydroxymethylfurfural (HMF) yield over time in the deep eutectic systems consisting of tetraethyl ammonium
chloride and levulinic acid (TEAC:LA 1:2) with different catalysts. The catalysts were added to the fructose+DES mixture
undissolved as a powder. Reaction temperature: 323 K; wFRU,0 = 2.5 wt.%. Symbols present yields in different reaction
medium: circles: TEAC:LA with HPA 5; stars: TEAC:LA without catalyst.